Detergent acid salts of certain imidazolinium compounds



Ma i-I United States Patent DETERGENT ACID SALTS OF CERTAIN llVIlDAZOLINIUM COMPOUNDS Hans S. Manuheimer, New York, N. Y.

No Drawing. Application June 21, 1956, Serial No. 592,749

13 Claims. (Cl. 260-3096) This invention relates to novel compositions and to methods for producing them. In one of its more specific aspects the invention is directed to methods of making and to novel derivatives of metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates, examples of which are disclosed in my U. S. Patent 2,528,378 and which I shall hereafter refer to herein as cycloimidates.

Said cycloimidates have been found useful because they have high detergent, foaming, wetting, emulgating, emulsifying, dispersing, bacteriastatic, bacteriacidal, fungicidal, and deodorizing characteristics. They are highly water-soluble, stable in aqueous solutions in the pH range of l-14 and are not precipitated out of solution by the salts normally present in hard water. They are nonvesicant and non-toxic to human and animal life and may be introduced into the blood stream without ill effects. They are surface active agents and serve as excellent synthetic detergents, softeners and dye assistants in the textile and related fields and especially in washing and cleansing of cotton fibers and textiles. They may also be employed as therapeutic agents and are especially useful as germicides, fungicides and antisepticides.

Said cycloimidates have the following general formula:

FORMULA I in which R is the organic radical which if connected to a carboxyl group provides a monocarboxylic acid and said radical contains at least 4 carbon atoms; R2 is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, such as CH2--, C2H4-, C3Hs, and C4Ha-- or any of the aforesaid groups, any one or more of whose hydrogens may be hydroxy substituted, illustrative examples of which are or any one of the aforesaid groups either unsubstituted or hydroxy substituted and having a single ether (-O) or keto (--CO) linkage therein, illustrative examples of which are c I both M radicals may be the same as or different from each other and each is a metal and preferably an alkali metal and for most purposes is sodium or potassium.

The methods for producing said"cycloimidates" and ms Ce 2,781,358

Patented Feb. 12, 1957 illustrative examples of a number of specific cycloimidates are disclosed in said patent.

Prior to this invention, it was known that cationic surface active agents and anionic surface active agents when together in aqueous solution resulted in the production or formation of water insoluble compounds; and that adding an anionic surface active agent to an aqueous solution of another anionic surface active agent resulted in a mere physical combination of said agents and that no reaction would occur between them.

Said cycloimidates normally behave anionically in aqueous solutions having a pH above 7, and consequently it was expected that said cycloimidates when in aqueous solution together with anionic surface agents that they would be combined physically only and that no other reaction would occur therebetween. In the course of my experimentations, I have discovered that said cycloimidates could be reacted with certain anionic surface active agents at a pH above 7 to produce water-soluble reaction products. Not only did I make said discovery, but I further discovered that water solutions of such reaction products had viscosities greater than corresponding aqueous solutions of the cycloimidates and also exhibited better foaming characteristics than did said cycloimidates in very low dilutions under extreme water hardness conditions. Said reaction products are non-toxic and non-irritating to the human skin. They have been found eminently useful as general utility detergents, such as for car washing, dish washing, clothes washing, etc. Said cycloimidates when used as components of shampoos sometimes caused slight irritation or stinging of the eyes when such shampoos were used and water solutions thereof accidentally reached the eyes. I have further discovered that the reaction products of this invention caused practically no irritation or stinging of the eyes when so employed.

According to this invention, one or a combination of two or more of said cycloimidates of the general structural Formula I are reacted with one or a combination of two or more anionic surface active agents of the following general structural Formula II to provide novel, water-soluble compounds having the following general structural Formula III, and having high wetting, detergency and surface active properties and capable of providing voluminous and stable foams in aqueous solutions, and which aqueous solutions are substantially non-irritating to the skin and eyes of normal human beings.

FORMULA n R3Z(C2H4O)a-SOQM FORMULA III wherein R3 is a hydrocarbon radical, generally aliphatic or aliphatic-aromatic, and having at least 5 carbon atoms and for most purposes 6-20 carbon atoms; Z is either oxygen or sulphur; and x is an integer and being at least 1 and generally l5, and preferably 3; M, R and R2 have heretofore been defined in Formula I.

According to this invention, I react a compound of Formula I with a compound of Formula II to provide the novel and highly useful compounds of Formula III. In general this reaction is carried out in a solution containing compounds I and II and to which a quantity of an acidic agent such as a strong mineral acid, as for example hydrochloric, sulphuric or its equivalent, has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approximately 100-200 F. In'this reaction under the aforesaid conditions, the quaternary hydroxy of the compound of Formula I combines with the metal of the compound of Formula II to produce the metal hydroxy and the metal of the OM group of the compound of Formula I is replaced by hydrogen due to the acidic agent addition which also at least in part reacts with the formed metal hydroxy compound to form a Water-soluble salt. The resultant solution can be used directly as a surface active agent, Wetting agent or detergent for the purposes indicated for the cycloimidates. While the quantities of the compound of Formula I and compound of Formula II may be equimolecular for good yield of compounds of Formula III, I may employ an excess of either, and in general the mole ratio of a compound of Formula .I to compound of Formula II may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out an aspect of this invention is to first dissolve a compound of Formula I in water and then the pH thereof is adjusted to approximately 12-13 (measuredele-ctrically) by the addition of aqueous caustic soda if required so that when a compound of Formula II is added thereto, the pH of the solution of I and II will be at least 10 and generally 10.5-11. The temperature of said solution is raised to 100-20G F. and preferably in factory practice to approximately 140 F. Then a quantity of a compound of Formula II is dissolved in Water in a separate container and this solution is added to said first solution and the mass is maintained in said temperature range while being constantly stirred, and an acidic agent is added thereto to reduce the pH thereof to a value below 10 and in the range of approximately 7 to 9, and preferably of approximately 8.2 to approximately 8.7. At the end of the acidic agent addition the stirring is continued and the temperature of the mass maintained for about 10-20 minutes after which the solution is allowed to :cool and is a finished product.

The following are specific examples merely given by way of illustrating the invention and are not to be taken by way of limitation, all parts being given by Weight unless otherwise specified.

Example 1 An aqueous solution of 400 parts of the lauric cycloimidates, of Example 1 of my heretofore identified patent, in 600 parts of Water is heated to approximately 140 F. and its pH (measured electrically) is adjusted by the addition of aqueous caustic soda to 12-13. While being constantly stirred and maintained at that temperature there is added a solution of 400 parts of sodium salt of lauryldiethoxyether sulfate:

C12:l2s-O-( C2H4O 2SOa-Na in 600 parts of water. Then while stirring and the temperature is maintained there is added thereto between about 3040 parts of hydrochloric acid solution (32%) whereby the pH of the mass is lowered to a value in the range of 8.2 to 8.7. Stirring is continued and the temperature maintained for about 10 minutes more. The

resultant product is a solution of the novel reaction product having the following formula:

Employ the same procedure and components as set .forth in Example 1 except that only about 200 parts of the sodium of lauryldiethoxyether sulfate are used. In this instance the resultant product is a solution of the reaction product whose structural formula is shown in Example 1 together with unreacted lauric cycloimidate" used, in the approximate proportion of two parts of the former to one of the latter.

Employ the same procedure as that set forth in Example 1, but employ the components indicated in the following Examples 3-8; the quantity of hydrochloric acid solution (32%) is variable to lower the pH to values indicated in Example 1 to obtain the reaction products of said Examples 3-8. 7

Example 3 400 parts of lauroyl cycloimidate (same as Example 1) in 600 parts of water. 250 parts of hexylmonoethoxyether sodium salt:

in 400 parts of water.

FORMULA OF REACTION PRODUCT CH2 N CH2 l CzH4OH CnH23-C---N OHz-OOONa OziHisO(C21-I4O)SO3 Example 4 350parts 10f caproyl cycloimidate of Example 3 of my hereinbefore identified patent in 650 parts of water. 400 parts of decyltriethoxythicether sulfate sodium salt:

400 parts of lauryl cycloimidate (same as Example 1) in 600 parts of water.

400 parts of nonylphenyltriethoxyether sulfate sodium in 600 parts of Water.

FORMULA OF REACTION PRODUCT CH2 i N CHz O2H4-OH Example 6 OH2OOONa 400 parts of lauroyl cycloimidate (same as Example 1) in 600 parts of water.

400 parts of octylphenyltetraethoxythioether sulfate sodium salt:

in 600parts of water.

FORMULA OF REACTION PRODUCT N CH:

Crflr-OH CnHaa- CHPCOONII Example 7 500 parts of amylphenylpentaethoxythioether sulfate sodium salt:

dissolved in 750 parts of water I FORMULA OF REACTION PRODUCT CH: N CH: l l OaHr-OH CuHv- -N CHr-C o ONa Example 9 400 parts of lauric cycloimidate of Example 1 of said patent in 600 parts of water.

450 parts of sodium salt of lauryl triethoxy ether sulfate:

C12H25O-( C2H4O aSOsNa in 700 parts of water.

FORMULA F REACTION PRODUCT N CH:

C2H4-OH C11Hasl-N The specific cycloimidates" used in Examples l-9 herein may be replaced by any of the other specific cycloimidates of my hereinb-efore identified patent, such as those of Examples 2, 4, 5, 7, -14 therein; and in addition the specific reactants I may differ from those employed herein in the radical R which may be a hydrocarbon radical of less or more carbon atoms, but in all cases being at least 4 carbon atoms and preferably 4-18 carbon atoms, and also other hydrocarbon radicals Rs than those specifically used herein may also be employed to provide a great variety of specific compounds illustrating the present invention.

It is to be understood that instead of first adjusting the pH of the cycloimidate to 12-13 before the addition of the compound of Formula II, any other method may be employed to obtain the condition whereby the pH of the solution of I and H is at least 10 and preferably 10.5-11 before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approximately 9. For example, I and II may be dissolved together and this solution may by the addition of caustic soda when required have its pH adjusted to at least 10, and then at l00-200 F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution at pH of at least 10 is brought to a temperature in the range of -200 F.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense. i

It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

This application is a continuation-in-part of copending application S. N. 425,307, filed April 23, 1954, now aban doned.

I claim:

l. A novel compound of the following formula:

in which R is a hydrocarbon radical of 4 to 18 carbon atoms; R2 is an organic group selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms, (b) hydroxy substituted aliphatic hydrocarbon groups of l-4 carbon atoms, (c) aliphatic ether groups, each of said groups having a single ether linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ether groups, each of said groups having a single ether linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic keto groups each of said groups having a single keto linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (1) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, R3 is a hydrocarbon radical of 6 to 20 carbon atoms; Z is an atom selected from the group consisting of oxygen and sulphur; x is a number of at least 1 and no greater than 5, and M is an alkali metal.

2. A novel compound of the following formula:

a-O-(CzHtO) r-SO:

in which R is a hydrocarbon radical of 4 to 18 carbon atoms, R3 is a hydrocarbon radical of 6 to 20 carbon atoms and x is 1-5.

3. An'ovel compound 'otthe'followin' a iH4 )=-S0:

in which R is a hydrocarbon radical of 4 to 18 carbon atoms, R3 is a hydrocarbon radical of 6 to carbon atoms, and x is 1-5.

4. A novel compound of the following formula:

in which R3 is a hydrocarbon radical of '6 to 20 carbon atoms and x is l-S.

5. .A novel compound of the following formula:

l Rr-S-(CQLO) 2-50;

onmO-o-wmron-so;

7. A novel compound of the following formula:

3 8. The method comprising under pH conditions of approximately 7 to approximately 9 reacting with each other compounds of the following Formulas I and II:

FORMULA I FORMULA II in which R is a hydrocarbon radical of 4 to 8 carbon atoms; R2 is an organic group selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms, ([2) hydroxy substituted aliphatic hydrocarbon groups of 1-4 carbon atoms, (0) aliphatic other groups, each of said groups having a single ether linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ether groups, each of said groups having a single ether linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic keto groups each of said groups having a single keto linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (f) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, R3 is a hydrocarbon radical of 6 to 20 carbon atoms; Z is an atom selected from the group consisting of oxygen and sulphur; x is a number of at least 1 and no greater than 5, and M is an alkali metal.

9. The method comprising to a solution containing a compound of Formula 'I anda compound of Formula II both defined in claim 8, adding a quantity of an acidic agent to lower the pH thereof to a valued approximately 7 to approximately 9-and maintaining the temperature of the mass between about F. and 200 F.

10. The method comprising to a solution whose pH is at least 10 and containing a compound of Formula I and a compound of Formula II both defined in claim 8, adding a quantity of an acidic agent to lower the pH thereof to a value of approximately 7 to approximately 9 and maintaining the temperature of the mass between about 100 F. and 200 F.

11. The method defined in claim 8, with the mole ratio of compound of Formula I to compound of Formula 11 being 2 moles of the former to 1-3 moles of the latter.

12. The method defined in claim 9, with the mole ratio of compound of Formula I to compound of Formula Ii being 2 moles of the former to l-3 moles of the latterv 13. The method defined in claim 10, with the mole ratio of compound of Formula I to compound of Formula II being 2 moles of the former to 1-3 moles of the latter.

No references cited. 

1. A NOVEL COMPOUND OF THE FOLLOWING FORMULA: 